Biocatalytic devices

Background current, 21, 65 Background subtraction, 40, 106 Bacteria electrode, 182 Band microelectrodes, 130, 135 Beryllium, 82 Bienzyme electrodes, 175 Biocatalytic devices, 172 Biological recognition, 171 Biosensors, 50, 171 Bipotentiostat, 106 Blood electrolyte, 165 Boltzmann equation, 19 Brain analysis, 40, 116 Butler-Volmer equation, 14... 

Many assembled glucose-02 biocatalytic fuel cells have been reported in recent years. This section aims at giving an overview of the methods that have been used to build these biocatalytic fuel cells and of the performances obtained by these devices depending on their different designs. 

A remaining crucial technological milestone to pass for an implanted device remains the stability of the biocatalytic fuel cell, which should be expressed in months or years rather than days or weeks. Recent reports on the use of BOD biocatalytic electrodes in serum have, for example, highlighted instabilities associated with the presence of 02, urate or metal ions [99, 100], and enzyme deactivation in its oxidized state [101]. Strategies to be considered include the use of new biocatalysts with improved thermal properties, or stability towards interferences and inhibitors, the use of nanostructured electrode surfaces and chemical coupling of films to such surfaces, to improve film stability, and the design of redox mediator libraries tailored towards both mediation and immobilization. 

Besides the broad applications of electrically contacted enzyme electrodes as amperometric biosensors, substantial recent research efforts are directed to the integration of these functional electrodes as biofuel cell devices. The biofuel cell consists of an electrically contacted enzyme electrode acting as anode, where the oxidation of the fuel occurs, and an electrically wired cathode, where the biocatalyzed reduction of the oxidizer proceeds (Fig. 12.4a). The biocatalytic transformations occurring at the anode and the cathode lead to the oxidation of the fuel substrate and the reduction of the oxidizer, with the concomitant generation of a current through the external circuit. Such biofuel cells can, in principle, transform chemical energy stored in biomass into electrical energy. Also, the use... 

Metallic nanoparticles and single-walled carbon nanotubes (SWCNTs) exhibit nanoscale dimensions comparable with the dimensions of redox proteins. This enables the construction of NP-enzyme or SWCNT-enzyme hybrids that combine the unique conductivity features of the nanoelements with the biocatalytic redox properties of the enzymes, to yield wired bioelectrocatalyts with large electrode surface areas. Indeed, substantial advances in nanobiotechnology were achieved by the integration of redox enzymes with nanoelements and the use of the hybrid systems in different bioelectronic devices.35... 

Methods to electrically wire redox proteins with electrodes by the reconstitution of apo-proteins on relay-cofactor units were discussed. Similarly, the application of conductive nanoelements, such as metallic nanoparticles or carbon nanotubes, provided an effective means to communicate the redox centers of proteins with electrodes, and to electrically activate their biocatalytic functions. These fundamental paradigms for the electrical contact of redox enzymes with electrodes were used to develop amperometric sensors and biofuel cells as bioelectronic devices. 

In order to increase the efficiency of biocatalytic transformations conducted under continuous flow conditions, Honda et al. (2006, 2007) reported an integrated microfluidic system, consisting of an immobilized enzymatic microreactor and an in-line liquid-liquid extraction device, capable of achieving the optical resolution of racemic amino acids under continuous flow whilst enabling efficient recycle of the enzyme. As Scheme 42 illustrates, the first step of the optical resolution was an enzyme-catalyzed enantioselective hydrolysis of a racemic mixture of acetyl-D,L-phenylalanine to afford L-phenylalanine 157 (99.2-99.9% ee) and unreacted acetyl-D-phenylalanine 158. Acidification of the reaction products, prior to the addition of EtOAc, enabled efficient continuous extraction of L-phenylalanine 157 into the aqueous stream, whilst acetyl-D-phenylalanine 158 remained in the organic fraction (84—92% efficiency). Employing the optimal reaction conditions of 0.5 gl min 1 for the enzymatic reaction and 2.0 gl min-1 for the liquid-liquid extraction, the authors were able to resolve 240 nmol h-1 of the racemate. 

Organization of biocatalytic photosynthetic systems in the form of integrated assemblies could provide practical photosynthetic devices. ET-communication of the cofactor or artificial electron shuttle with the enzyme active site proceeds in solution by a diffusional mechanism. An integrated biocatalytic photosynthetic device that allows the continuous light-induced production of fuel materials or... 

The second device was a multiplate-stacked microfluidic reactor, originally developed by Hessel, Lowe and co-workers for gas-phase transformations [lb] (Figure 3.2) and now adapted for biocatalytic processing with immobilized enzymes. 

Command surfaces based on isomerizable monolayers have also been used to detect various signals (temperature change [204], pH change [205]) by the variation of redox cofactor regeneration rates (therefore by the control of enzymatic activity). Thus, they represent examples of biocatalytic switches. All the systems described above represent examples of bioelectronic devices that can be used for the trans-... 

Water content <50 ppm. Solvents for organic and biocatalytic reactions, electrolytes for electrochemical devices. 

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